Cyanophenyl o,s-dialkyl phosphorothiolates

ABSTRACT

Optionally halogenated cyanophenyl O,S-dialkyl phosphorothiolates, i.e. cyanophenyl or halocyanophenyl O,Sdialkyl phosphorothiolates wherein one of the alkyl groups may be cycloalkyl, alkyl of 4-6 carbon atoms, a chlorine-substituted lower alkyl group or a phenyl group and the other alkyl group is methyl or ethyl, which thiolphosphates possess microbicidal, especially fungicidal properties.

United States Patent [191 Kishino et al.

[ CYANOPHENYL O,S-DIALKYL PHOSPHOROTHIOLATES [75] Inventors: Shigeo Kishino; Yasuo Yamada';

Yoshio Kurahashi; Toyohiko Kume, all of Tokyo, Japan [73] Assignee: Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany 22 Filed: Jan. 5, 1971 21 Appl.No.: 104,177

[30] Foreign Application Priority Data Jan. 8, 1970 Japan 45/2286 [52] US. Cl. 260/940, 424/210 [Sl] Int. Cl. C07f 9/18, AOln 9/36 [58] Field of Search 260/940 June 26, 1973 [56] References Cited UNITED STATES PATENTS 3,309,371 3/1967 Curry et al 260/940 Primary ExaminerLewis Gotts Assistant Examiner-Anton l-l. Sutto Att0rneyBurgess, Dinklage & Sprung [5 7] ABSTRACT 18 Claims, No Drawings CYANOPHENYL O,S-DIALKYL PHOSPHOROTHIOLATES The present invention relates to and has for its objects the provision of particular new optionally halogenated cyanophenyl O,S-dialkyl phosphorothiolates, i.e.

cyanophenyl or halocyanophenyl O,S-dialkyl phos-' phorothiolates wherein one of the alkyl groups may be cycloalkyl, alkyl of 4-6 carbon atoms, a chlorinesubstituted lower alkyl group or a phenyl group and the other alkyl group is methyl or ethyl, which phosphorothiolates possess microbicidal, especially fungicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for using such compounds in a new way especially for combating microorganisms, especially fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

The specification of Japanese Patent Publication No. 16875/63 discloses that O,S-dialkyl-O-substituted phenylphosphorothiolates have insecticidal activity. However, there is nothing to lead one to expect that these compounds might have fungicidal properties or that they might be useful as fungicides and bactericides.

It has now surprisingly been found that the new S-alkyl-O-alkyl-O-cyanophenyl phosphorothiolates of the general formula R S Y RIS (II) is reacted with a phenol derivative of the general formula Y (III) wherein R, R and Y have the same meanings as in formula (l) and M is hydrogen, a metal or ammonium.

As is apparent from the general formula (I), the compounds of this invention have a structure characterized in that the groups R and R are asymmetric, and they exhibit excellent fungicidal activity, though their insecticidal activity is inferior as compared with analogous phosphate compounds of the type disclosed in Japanese Patent Publication No. 16875/63.

The compounds of this invention exhibit high activity against pathogenic fungi causing diseases of plants and are excellent in that they are effective against fungi of a broad range. Further, these compounds have low toxicity to warm blooded animals and possess suitable affinity with higher plants, not being phytotoxic to higher plants at ordinary application concentrations. Accordingly, the compounds of this invention can be used suitably as agricultural and horticultural agents for preventing and controlling diseases of plants caused by fungi.

More specifically, the compounds of this invention can be used as fungicides for protecting plants from damage caused by Archimycetes, Phycomycetes, Ascomycetes, Basidiomyceres, Fungi Imperfecti and other fungi.

The active compounds of this invention can be applied for controlling pathogenic fungi living in the above ground portions of plants, pathogenic fungi invading plants from the soil and causing tracheomycosis, seed-borne pathogenic fungi and soil-infectious pathogenic fungi.

The above-mentioned excellent characteristics enable the active compounds of this invention to give good results when applied against diseases caused by those pathogenic-fungi that have had to be controlled by fungicides containing heavy metals harmful to men and domestic animals, such as arsenic and mercury. Further, they give particularly good results in controlling pathogenic fungi and bacteria causing diseases of rice plants. More particularly, these compounds exhibit excellent activity against Piricularia oryzea causing blast on rice plants and Pellicularia sasakii causing sheath blight, and they may be used for controlling both these organisms simultaneously. The compounds exhibit curative activity as well as preventive activity.

Further, the compounds of this invention exhibit good controlling effects against fungi and bacteria which infect rice plants and other agricultural plants such as Xanthomonas oryzae causing bacterial leaf blight on rice plants, Ervinia aroideae causing bacterial soft rot on chinese cabbage, Xanthomonas citri causing canker on citrus fruits, Cochliobolus miyabeanus causing brown spot on rice plants, Mycosphaerella musicola causing leaf spot on bananas, Botrytis cinerea causing gray mold on strawberry and other plants, Plasmopara viticola causing downy mildew on grapes, Glomeralla cingulata causing anthracnose on grapes, apples and pears, Sclerotinia sclerotiorum causing stem rot on vegetables, Colletotrichum lagenarium causing anthracnose on melons, Diaporthe citri causing melanose on citrus fruits, Podosphaera Ieucotricha causing powdery mildew on apples, Sphaerotheca fuliginea causing powdery mildew on cucumbers, Alternaria mali causing cork spot on apples, Alternaria solani causing early blight on potatoes, Alternaria kikuchiana causing black spot on pears, Venturia inaequalis causing scab on apples and Venturia pirina causing scab on pears.

As described above, the compounds of this invention exhibit excellent effects in the control of pathogenic fungi damaging rice plants and other cultivated plants. Accordingly, the compounds of this invention are very valuable in saving the labor needed to remove diseased plants to prevent their infection of healthy plants.

The phosphoric acid triesters of this invention are novel compounds which have now been synthesized for the first time. The preparation is illustrated by the following formula scheme:

Examples of R are n-, iso-, secor tert-butyl or pentyl or hexyl, cyclopentyl, cyclohexyl, chloromethyl, chloro-ethyl, 2,2,2-trichloroethyl, l-methyl-Z- chloroethyl, l-methyl-3-chloropropyl, l-chloromethyl-Z-chloroethyl, l-methyl-Z-chloropropyl, l-methyl-3-chloropropyl and phenyl. R is preferably ketones and nitriles such as acetone, methylethylketone, methylisopropylketone, methylisobutylketone, acetonitrile and propionitrole; n-, isoor sec-butyl, cy' clohexyl, 2-chloroethyl, l-methyl-Z-chloroethyl, l-chloromethyl-2-chloroethyl or phenyl.

Y is hydrogen atom or halogen such as fluorine, chlorine, bromine and iodine. Preferably, it is hydrogen, chlorine or bromine.

As examples of the phosphoric acid diester' monohalides of formula (II), there may be mentioned O-n- (isoor sec-) butyl-S-methyl-, O-n-(isoor sec-) butyl- S-ethyl-, O-cyclo-hexyl-S-methyl (or ethyl)-, O-phenyl- S-methyl (or ethyl)-, O- (2-chloro)ethyl-S-methyl, O- l-methyl-2-chloro)ethyl-S-methyl or ethyl)- and O- l-chloromethyl-2-chloro)ethyl-S-methyl (or ethyl)-thiolphosphoryl chlorides.

As examples of the phenol of formula (III) there may be mentioned 2-(or)4- cyanophenol, 2-cyano-4- chlorophenol, 2- cyano-4-bromophenol and 2-chloro- 4-cyanophenol, and salts of these phenols with ammonium or a metal such as sodium or potassium.

The reaction is preferably carried out in the presence of a solvent which term includes a mere diluent. Any inert solvent may be used for this purpose. Particularly good results are attainable with the use of aliphatic and aromatic hydrocarbons which may be chlorinated, such as methylene chloride, di-, triand tetrachloroethylenes, chloroform, carbon tetrachloride, benzine, benzene, chlorobenzene, toluene and xylene; ethers such as diethyland di-n-butyl ethers, dioxane and tetrahydrofurane; low molecular weight aliphatic ketones and nitriles such as acetone, methylethylketone, methylisopropylketone, methylisobutylketone, acetonitrile and propionitrile; low boiling aliphatic alcohols such as methanol and isopropanol; and the like.

The reaction may be conducted in the presence of an acid binder. Compounds which are usually usedas acid binder, for instance hydroxides, carbonates, bicarbonates and alcoholates of alkali metals and tertiary organic bases, such as triethylamine, dimethylaniline and pyridine, may be used.

When the reaction is effected in the absence of an acid binder, the intended product of high puritiy can be also obtained in high yield by forming a salt, preferably an ammonium or alkali metal salt, of the starting phenol in advance and then reacting the salt with the phosphoric acid diester monohalide.

The reaction of the invention may be performed over a broad temperature range. Generally, the reaction is carried out at temperatures ranging from about -20C to the boiling point of the reaction mixture. Preferably, the reaction is effected at about 0 C. it is preferable to conduct the reaction under atmospheric pressure but it is possible to carry out the reaction under reduced or elevated pressure.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e., diluents or extenders of the type usable in conventional pesticidal formulations or compositions, e.g. conventional pesticide formulation or composition such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, wettable powders, soluble powders, oil preparations, aerosol preparations, dusting agents, coated particles, tablets, granules, pellets, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, dimethylnaphthalene, aromatic naphthas, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chloro-benzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, carbon tetrachloride, chloroethylene, etc.), cyclohexane, alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), (amines(e.g. ethanolamine, etc.), ethers, ether-alcohols-(eg. glycol monomethyl ether, etc.), ketones (e.g. acetone, methylethylketone, cyclohexanone, etc.), strongly polar solvents such as acetonitrile, amides such as dimethyl formamide, sulfoxides (e.g. dimethyl'sulfoxide, etc. and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, attapulgite, clays, montmorillonite, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.), whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (eg polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkylaryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.; as will as gaseous diluents or carriers such as freon and other aerosol propellents which are gaseous under normal conditions.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as acaricides, insecticides, nematocides, rodenticides, plant growthregulating agents, or fungicides (including antibiotic substances), herbicides, bactericides, etc., as will as fertilizers, if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules whichare thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95 percent by weight, and preferably 0.5-90 percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct appliction or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-20 percent, preferably 0.01-5 percent by weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of carrier vehicle assistant e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95 percent, and preferably 0.01-95 percent, by weight of the mixture.

The active compounds can also be used in accordance with the well known u1tra-1owvo1ume process with good success, i.e., by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment in finely divided form, e.g. average particle diameter of form 50-100 microns, or even less i.e'. rnist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, generally about to 1,000 g per hectare, preferably about 40 to 600 g per hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about to about 95 percent by weight of active compound or even the 100 percent active substance alone, e.g. about 20-100 percent by weight of the active compound.

In particular, the present invention contemplates methods of selectively killing, combating or controlling the pests, e.g. fungi, and more particularly, methods of killing or controlling fungi which comprises applying to at least one of correspondingly (a) such fungi, and (b) their habitat, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. fungicidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, fumigating, injecting, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in the admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention is illustrated without limitation by the following examples.

EXAMPLE 1 l 1.9 g of 2-cyanophenol and 10.2 g of triethylamine were dissolved in 150 ml of benzene, and l 1.7 g of S- ethyl-O-n-butylthiolphosphoryl chloride were added dropwise to the solution at 1020C. with stirring. The stirring was continued for 2 hours at 2530C and for another hour at 50-60C. to complete the reaction. The reaction mixture was cooled, washed with water, 1% hydrochloric acid and 1% aqueous sodium carbonate and dried over anhydroussodium sulfate. The benzene was removed by distillation and then the reaction mixture was subjected to distillation under reduced pressure to yield 22 g of S-ethyl-O-n-buty1-O-(2- cyanophenyl) phosphorothiolate of the formula:

C H S (24) The product was characterized by boiling point of 162C./0.3 mm Hg and a refractive index u of 1.521 1.

This compound is listed in Table 1 along with others which can be prepared by analogous methods. In that table, the compounds are identified by the indication of the specific meanings of R, R and Y and the position of the nitrile groups and of Y in formula (1).

TABLE 1 j C d N R R CN Y Plysgcal properties: Boiling point (refractive ompoun o. 7 1n ex 1 n-CtH CH; Z-CM H 13.1. bis-160 C./0.1 mm. Hg (1213 1.5258). 2 2-CN 4-01 B.P. 156 C./0.2 mm. Hg (111:) 1.5358).

4-CN H B.P. 166 C./0.25 mm. Hg (1113 1.5290). 4-ON 2-01 B.P. 166-168 C./0.1 mm. Hg (no 1.5400). 2-CN H B.P. 155 C./0.1 mm. Hg (1)" 1.5254). 2-CN H B.P. 155 C./0.1 mm. Hg (1111 15271).

2-CN H B.P. 155 C./0.1 mm. Hg (1m 1.5432).

2-cN 4:01 B.P. 155 o. o.1 mm. Hg (1111 15520). 4-CN II 13.1. 155 C./().1 mm. 11;; 1.5470 $01 13.1 ()./0.1 mm. Hg (710 15552).

z-oN H B P 01 025 mm. Hg ms 1.539s).

13. Same as above CH; 2-CN 4-01 B .P 171 C./0.1 mm. Hg (7113 1.5520). 14-. d0 CH3 4-CN H B.P. 173 C./0.'15 mm'. Hg (1113 15463). 15. d0 CH3 4-CN 2-01 B.P 173 C./0.15 mm. Hg (m) 1.5591).

10 ClCHaCHzCH- CH; Z-CN H TABLE 1 3Hi503"" Physical properties: Boiling point (refractive Compound No. R1 R2 ON Y index) 17 Same as above CH3 2-CN 4-01 111.... .110 CH3 4-CN H 111 "do CH3 4-CN 201 20 Q CH3 2-0N H B.P. 177-170 0. o.15 mm. Hg 119 1.5795

b CH 2-CN 4-01 B.P. 179-1s0 0. o.15 mm. H 110 1.5378).

CH: 4-011 H 11.1 185 070.03 mm. H (711 1-5832). 23"" .I d0- 4-010 201 B.P. 185 070.03 mm. H 111. 1.5802 23" ..do 4-CN 2-01 13.1 155 070.03 mm. Hg 1113 15022).

n-otHg 0,111 2-CN H B.P. 102 070.3 mm. H 1111 1.5211). 25 Same as above- 2-CN 1-01 15.1 ins-158 070.25 mm. H 115 1.5318 20" do 4010 H 15.1 155-150 0./0.1 mm. 11 (115 1.5234 27" .410... 4-051 201 B.P. 164-165 0./0.15 mm. 11 110 1.5345 2s" Isa-01111 11-05: H 111. 117 0.10.2 mm. H 115 1.5214 20:: Sec-04H 201v H 13.1. 147 0. 0.2 mm. H 59 1.52 11 30..-- Same as above C H 2-CN 4-01 13.1. 147 C./0.2 mm. Hg (711) 1.6330).

31 0,11 20N H B.P. 147 0.10.2 mm. H (175 1.5390).

2 b 0 H 2-ON +01 B.P.147 0.10.2 mm. H 111, 1.5558). 0:11: 4-CN H 13.1 117 0./0.2 mm. Hg 55 1.5430). 34 do 0,11, 405: 2 01 B.P.147 0.10.2 mm. Hg (7113 1.5500). 35 ClCH CH- 0,11 2-CN H B.P.160163 0./0.2 mm. Hg 115 1.5357).

2- N 4- 13.1. 180 040.4 mm. H 115 1.5450 2911: "IIILI same as above CZHS 4-817 H B.P. 178 070.3 mm. Hg (21.133 1.5407 38..-. 4-010 201 B.P. 17s" 0./0.a mm. H 115 1.5547). 30.--- 2010 4-31 B.P. 178 070.3 mm. H (7113 1.5040) 40..--

010111110H- 2-CN H B.P.175 0.10.05 mm. H 115 1.5190) 41 Same as above CgHg 2-CN 4-C1 B.P. 175 C./0.05 mm. Hg (711)" 1.5575).

42 Q 0,11 2010 H 13.1. 170 010.13 mm. H 110 15720).

b 0 H Z-CN 4-01 13.1 190 0. o.2 mm. H 115 1.5709). 43 as a We 2 5 4-057 H B.P. 175 0. 0.07 mm. Hg (7111 16768). 4-CN 2-01 13.1 175.0. o.07 mm. H 50 1.5530).

EXAMPLE 2 15 parts by weight of compound (l7) of Table l, 80 parts by weight of diatomaceous earth and 5 parts by weight of an emulsifier (i.e. polyoxyethylene alkylaryl ether) are mixed and crushed to prepare a wettable powder. This formulation may be diluted with water to the desired concentration and then be used as a ready-to-use-preparation.

EXAMPLE 3 parts by weight of compound (7) of Table l, 30 parts by weight of xylene, 30 parts by weight of Kawakasol (an aromatic hydrocarbon with a boiling range of 150 to 200C.) and 10 parts by weight of the emulsifier Sorpol (i.e. polyoxyethylenealkylaryl ether) are mixed and stirred to prepare an emulsifiable con centrate (an emulsifiable liquor). This formulation may be diluted with water to the desired concentration and then used as a ready-to-use-preparation.

EXAMPLE 4 To a mixture consisting of 10 parts by weight of compound (24) of Table 1, 10 parts by weight of bentonite, 78 parts by weight of a mixture of talc and clay (1:3) and 2 parts by weight of lignin sulfate, 25 parts by weight of water are added and the mixture is firmly kneaded. it is finely cut into granules of 0.5 to L5 mm diameter by means ofa granulating machine. The granules are then dried at a temperature between 40 to 50C to obtain a granular formulation. This formulation may directly be applied to the soil.

EXAMPLE 5 2 parts by weight of compound (27) of Table l and 98 parts by weight of a mixture of talc and clay (1:3)

are mixed and crushed to prepare a dust. This formulation may directly be used as a ready-to-usepreparation.

EXAMPLE 6 Test on blast of rice plants (Piricularia oryzae):

Preparation of sample chemical liquor Solvent: 1 part by weight of acetone Dispersing agent: 005 part by weight of sodium oleate Other additive: 0.2 part by weight of gelatin Water: 98.75 parts by weight A concentrated emulsifiable liquor (obtained by adding the active compound in an amount sufficient to ob tain the prescribed concentration to the above amount of the solvent) was admixed with the above amount of water containing the above amounts of the dispersing agent and gelatin.

Test procedures a. Test of preventive effect and the durability of effect (residual effect):

Rice plant (jukkoku variety) was cultivated in a pot of 12 cm diameter and the above-mentioned diluted liquor containing the active compound of this invention at the prescribed concentration was applied to the rice plant in the amount of 50 ml per 4 pots.

One half of the chemical-sprayed rice plant was kept in a chamber maintained at 25C and a relative humidity of percent for 2 days from the next day after the chemical spraying and the remaining half was kept in the same chamber for 2 days from the fourth day after the chemical spraying. While in the chamber, the rice plant was twice inoculated by spraying with a suspension of spores of artifically cultured pathogenic fungi of blast. From 'the results of the infection made the next day after the chemical spraying, the direct preventive effect can be evaluated, and from the results of the infection made the fourth day after the chemical spraying, the durability of the preventive effect (residual effect) can be ascertained.

Seven days after inoculation, the degree of infestation was determined by applying a scale ranging from to 5, and the protective value of each'particular active compound against Piricularia oryzae was determined in accordance with the formula below.

At the same time, the phytotoxicity against rice plants was determined.

Infested area of leaf in Degree of total leaf 1 2-5%. 2 3 l0-207c 4 -40% 5 40 or more% Protective value 100 Degree of infestation of treated plants/Degree of infestation of non-treated plants X 100 The active compounds tested and the average results obtained can be seen from the following Table:

TABLE 2 Results of tests on effects against blast of rice plant Active Protective value Compound component Pre- N o. concentraventive Residual Phytotoxicity tion (ppm) effect effect 8 250 lOO 78 500 I00 95 20 250 I00 75 500 I00 I00 28 250 100 74 500 I00 lOO (compari- 480 86 22 son) 5 treated 0 0 (control) Notes:

1. The compound numbers in the Table correspond to those in Table l.

2. Comparison is commercially benzylphosphorothiolate 3 The symbol in column Phyt0toxicity" means that the chemical did not adversely affect the growth of the rice plant.

EXAMPLE 7 Test of effect against sheath blight (Pellicularia sasakii):

Test procedures Rice plant (Kinmaze variety) was cultivated in a 12 cm diameter pot, and at the primary tillering stage the diluted liquor containing the active compound at the prescribed concentration, which was prepared in the same manner as in Example 6, was applied to the rice plant in an amount of 50 ml per 3 pots.

The next day, the root of the sample rice plant was inoculated withipathogenic fungi of sheath blight which had been cultured in a barley culture medium for 10 days and in which sclerotia had been formed. Then the sample was kept in a chamber maintained at 28-30C and a relative humidity of more than percent for 8 days. The degree of the disease was examined.

The degree of infestation was determined by means of the formula (1) and the protective value of each compound was calculated in accordance with the formula (2): Degree of infestation 3n, 2'n l-n '"o)/(3'N) X (1) available. 0,0-diisopropyl-S- wherein N the number of the total stems examined n the number of non-infested stems n the number of stems infested up to the first leaf (from the bottom) in the number of stems infested up to the second leaf (from the bottom) n;, the number of stems infested up to and above the third leaf (from the bottom) Protective value TABLE 3 Results of tests on sheath blight Active compound concentration pp Compound No. Protective value 21 Umreatemcontrol) ISO EXAMPLE 8 Plant Pathogens Test (Agar dilution method):

The active compound was mixed in an agar culture medium of potato to form the desired concentration of active compound therein. After the medium was poured into Petri dishes of 9 cm diameter and coagulated, the same were inoculated with the corresponding plant pathogens. A control Petri dish to which no active compound was added, was also set up. After having been cultured at a temperature of 27C for 4 days, the growth condition of the plant pathogens was investigated and the degree of illfungal growth was determined by applying a scale ranging from O to S as follows:

The active compounds tested and the average results obtained can be seen from the following Table:

Degree of illfungal growth by application of such compounds to such fungi and/or I their habitat.

It will be appreciated that the instant specification and examples are set worth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. Organic phosphoric acid esters of the general formula wherein R is an alkyl group with 4-6 carbon atoms, a cycloalkyl group, chlorine-substituted lower alkyl group or a phenyl group,

R is an alkyl group with one or two carbon atoms,

and

Y is hydrogen or halogen, the -CN and Y groups being present in the 2- or 4-positions.

2. (Zompounds according to claim 1 in which R is n-, iso or sec-butyl, cyclohexyl, 2-chloroethyl, l-methyl- 2-chloroethyl, l-methyl-3-chloropropyl, l-chloromethyl-2-chloroethyl or phenyl, and Y is hydrogen, chlorine or bromine.

3. Compound according to claim 1 wherein such compound is S-methyl-O-n-butyl-O-(2-cyanopehnyl) 0 not growth phosphorothiolate of the formula 1 2 20 percent of the non-treated mycerial area 2 percent C H O 0 C 3 percent 35 g 4 80 percent 0 5 the same growth as the non-treated area CHa-S (3) TABLE 4 Effects against various pathogenic microorganisms 01' plants Sclero- Concentinia- Collecto- Altertration Piricu- Pelli- Xantho sclcro trichum 'naria Diapor- Glomc- Scleroof active laria cularia 'mmms tzorum lagenakikuchithe rella tim'a ingredioryzae sasakii oryrae (vegerium ana citrz' cingulata cimrea Compound No. ent, p.p.m (rice) (rice) (rice) tables) (melon) (pear) (citrus) (grape) (peach) 3 800 0 0 0 0 0 0.5 0 0 0 200 0 O 0 O 0. 5 1 0 0. 5 0. 5 50 0 0 0. 5 2 I. 5 1 1 2 1 12. 5 0 0. 5 1 3 3 2 2 4 3 7 800 0 0 0 0 0 0 0 0 0 I 200 0 0 1 0 O. 5 0 0 O. 5 0. 5 50 0 0. 5 1. 5 0. 5 1 1 1 1 2 12. 5 0 1 2 1. 5 2 2 2 2 3 12 800 o 0 0 0 0 0 0 0 O 200 0 0 0 1 0. 5 0. 5 0. 5 l l 50 0 0. 5 1. 5 2 2. 5 l 1 2 2 l2. 5 0 2 2 3 3 2 2 3 3 27 800 0 0 0 0 U 0 0 0 0 200 0 0 0 0 U 0 0 0 (l. 5 50 0 0 O 0. 5 l 1 (l. 5 l l 12. 5 0 0. 5 0. 5 I Z 3 1. 5 l 2 3 Untreated (control) 5 5 5 5 5 5 5 5 5 4. Compound according to claim 1 wherein such compound is S-methyl-O-cyclohexyl-O-(2- cyanophenyl) phosphorothiolate of the formula 5. Compound according to claim 1 wherein such 12. Compound according to claim 1 wherein such compound is S-methyl-O-cyclohexyl-O-(2-cyano-4- compound is S-ethyl-O-n-butyl-O-(2-chloro-4- chlorophenyl) phosphorothiolate of the formula cyanophenyl) phosphorothiolate of the formula 5 H O 0 ON n-clm-o 0 Cl \1] A i o( CN P-O Cl c1ns (8) CHFS ('27) i 10 6. Compound according to claim 1 wherein such 13. Compound according to claim 1 wherein such compound is S-methyl-O-(l-methyl-2-chloroethyl)-O- compound is S-ethyl-O-isobutyl-O-(Z-cyanophenyl) (Z-cyanophenyl) phosphorothiolate of the formula phosphorothiolate of the formula CN CN ClCHAI'JH-O\CH) iso-C H 0 (1 CH3 /P0 1' -o CH3-S (12) C2H5S/ (28) 7. Compound according to claim 1 wherein such 14. Compound according to claim 1 wherein such compound is S-methyl-O-(l-methyl-2-chloroethyl)-O- compound is S-ethyl-O-sec.-butyl-0-(Z-cyanophenyl) (2-cyano-4-chlorophenyl) phosphorothiolate of the phosphorothiolate of the formula formula CgHr'S (29) CH;-S/ (13) 15. Compound according to claim 1 wherein such compound is S-ethyl-0-cyclohexyl-O-(2-cyanophenyl) 8. Compound according to claim 1 wherein such phosphomthiolate of the formula compound is S-methyl-O-(l-methyl-3-chloropropyl)- O-(Z-cyanophenyl) phosphorothiolate of the formula G O O 7 CN CN \u cicrnomcH-o o P4) (3H1 I -0Q CHIPS a (an cH1s (1e) 16. Compound according to claim 1 wherein such 9. Compound according to claim 1 wherein such 40 compound is y y y compound is S-methyl-O-(l-methyl-3-chloropropyl)- (2* y P "y Phosphorothiolate of the O-(2-cyano-4-chlorophenyl) phosphorothiolate of the formula formula 0N cur-S (17 17. Compound according to claim 1 wherein such compound is S-methyl-O-(l-chloromethyl-2- chloroethyl)-O-(2-cyano-4-chlorophenyl) phosphorothiolate of the formula 10. Compound according to claim 1 wherein such compound is S-methyl-O-phenyl-O-(2-cyanophenyl) phosphorothiolate of the formula CICH;

18. Compound according to claim 1 wherein such 11. Compound according to claim 1 wherein such compound is s ethyl o phenyl o (2 cyanophenyl) compound 18 y y y phosphorothiolate of the formula phosphorothiolate of the formula UNITED STATES PATENT OFFICE v (5/69) I: ra m r\ w w r CILRI II. ILA. l h 01 CORRLC I ION Patent No. 3,742,094 Dated June 26, 1973 fl) Shigeo Kishino et a1 I I It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

a Col 3', lines: 20-22 delete" "ketones .prtipionitroleg" g Col. 3, line 34, insert; pa 'enthesisbsfore or ethyl)". c

Col. 6, Table 1, Compound No, 1, change; "2-CM" to Z-CN Cols 6 snfi 7, .Tnble I, nudes-heading "Physical Properties delete boiling points from Compounds Nos. 6, 7, s, 9, 1o, 15, 23, 29, '30, 31,32, 33, 34, 3s,

39, 41 and 45; 20

mp a g fi 1,5254" to :1 1,5254

1 Delete Compound 23, first occurrence.

: Col.'ll,-line 13 .-'Table 3 under heading "Protective value" 3 insert -O for the "untrea t'e d control".

s01. 13, claim '10,. in the formula, delste "01'' at end of formula (20) Signed snd sealed this 28th day of January 1975.

(SEAL) Attest:

McCOY M. GIBSONJR. C. MARSHALL DANN Attesting Officer r Commissioner of Patents 

2. Compounds according to claim 1 in which R1 is n-, iso- or sec-butyl, cyclohexyl, 2-chloroethyl, 1-methyl-2-chloroethyl, 1-methyl-3-chloropropyl, 1-chloromethyl-2-chloroethyl or phenyl, and Y is hydrogen, chlorine or bromine.
 3. Compound according to claim 1 wherein such compound is S-methyl-O-n-butyl-O-(2-cyanopehnyl) phosphorothiolate of the formula
 4. Compound according to claim 1 wherein such compound is S-methyl-O-cyclohexyl-O-(2-cyanophenyl) phosphorothiolate of the formula
 5. Compound according to claim 1 wherein such compound is S-methyl-O-cyclohexyl-O-(2-cyano-4-chlorophenyl) phosphorothiolate of the formula
 6. Compound according to claim 1 wherein such compound is S-methyl-O-(1-methyl-2-chloroethyl)-O-(2-cyanophenyl) phosphorothiolate of the formula
 7. Compound according to claim 1 wherein such compound is S-methyl-O-(1-methyl-2-chloroethyl)-O-(2-cyano-4-chlorophenyl) phosphorothiolate of the formula
 8. Compound according to claim 1 wherein such compound is S-methyl-O-(1-methyl-3-chloropropyl)-O-(2-cyanophenyl) phosphorothiolate of the formula
 9. Compound according to claim 1 wherein such compound is S-methyl-O-(1-methyl-3-chloropropyl)-O-(2-cyano-4-chlorophenyl) phosphorothiolate of the formula
 10. Compound according to claim 1 wherein such compound is S-methyl-O-phenyl-O-(2-cyanophenyl) phosphorothiolate of the formula
 11. Compound according to claim 1 wherein such compound is S-ethyl-O-n-butyl-O-(2-cyanophenyl) phosphorothiolate of the formula
 12. Compound according to claim 1 wherein such compound is S-ethyl-O-n-butyl-O-(2-chloro-4-cyanophenyl) phosphorothiolate of the formula
 13. Compound according to claim 1 wherein such compound is S-ethyl-O-iso-butyl-O-(2-cyanophenyl) phosphorothiolate of the formula
 14. Compound according to claim 1 wherein such compound is S-ethyl-O-sec.-butyl-O-(2-cyanophenyl) phosphorothiolate of the formula
 15. Compound according to claim 1 wherein such compound is S-ethyl-O-cyclohexyl-O-(2-cyanophenyl) phosphorothiolate of the formula
 16. Compound according to claim 1 wherein such compound is S-ethyl-O-(1-methyl-2-chloroethyl)-O-(2-cyano-4-bromophenyl) phosphorothiolate of the formula
 17. Compound according to claim 1 wherein such compound is S-methyl-O-(1-chloromethyl-2-chloroethyl)-O-(2-cyano-4-chlorophenyl) phosphorothiolate of the formula
 18. Compound according to claim 1 wherein such compound is S-ethyl-O-phenyl-O-(2-cyanophenyl) phosphorothiolate of the formula 